CN108383684B - Synthesis method and system of 1, 3-butanediol - Google Patents

Synthesis method and system of 1, 3-butanediol Download PDF

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CN108383684B
CN108383684B CN201810266734.2A CN201810266734A CN108383684B CN 108383684 B CN108383684 B CN 108383684B CN 201810266734 A CN201810266734 A CN 201810266734A CN 108383684 B CN108383684 B CN 108383684B
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acetaldehyde
cracking
hydrogenation
butanediol
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CN108383684A (en
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夏春谷
朱刚利
王丹
郧栋
许传芝
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings

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Abstract

The invention discloses a method and a system for synthesizing 1, 3-butanediol. The synthesis method adopts a route of producing 1, 3-butanediol from acetaldehyde via 2,6-dimethyl-1, 3-dioxane-4-ol, improves the stability of an intermediate product, improves the selectivity of the 1, 3-butanediol, and reduces the generation of harmful crotonaldehyde and derivatives which are easy to develop color and smells. Meanwhile, the tubular reactor with built-in components is used as a condensation reactor, so that heat can be effectively removed, the low-temperature cooling load is reduced, the reaction controllability is improved, unnecessary back mixing is reduced, and the generation of byproducts is reduced. The invention adopts the mode of low-temperature flash evaporation and then catalytic reaction distillation to carry out 2,6-dimethyl-1, 3-dioxane-4-alcohol cracking and recover acetaldehyde, thereby effectively improving the utilization rate of raw materials, improving the yield of final products and ensuring that the chromaticity and odor can meet the requirements of most high-end applications.

Description

Synthesis method and system of 1, 3-butanediol
Technical Field
The invention relates to a synthesis method of 1, 3-butanediol (1,3-BDO), in particular to a synthesis method of 1, 3-butanediol and a system used by the same, belonging to the technical field of chemical industry.
Background
1, 3-butanediol is an important fine chemical as a diol, can be used as a raw material of polyester resin, alkyd resin and polyurethane, and can also be used as an excellent plasticizer. The 1, 3-butanediol has lower toxicity to higher animals than 1, 4-butanediol, is about equal to that of glycerin, has good moisturizing, antibacterial and antibacterial effects, and can be used for formulation of various high-grade cosmetics, ointment, surfactant and hygroscopic agent.
The common industrial routes for 1, 3-butanediol are: (1) condensing acetaldehyde under the condition of alkali catalysis and then hydrogenating; (2) a biological fermentation method; (3) the carbonylation of propylene oxide, the hydrogenation of beta-hydroxycarboxylic acid ester to obtain 1, 3-butanediol (old, quiet, parahongxiang, youneing, research on the cobalt-catalyzed carbonylation of propylene oxide to prepare beta-hydroxybutyrate, chemical report 2001,64: w 118.); (4) in addition, there are an acrolein method, an ethanol direct condensation method and the like. The methods have advantages and disadvantages, the acetaldehyde condensation hydrogenation method is the main production route at present, the gross profit rate of producing 1, 3-butanediol from acetaldehyde is high, and the method occupies the main market. The key technology of the 1, 3-butanediol is monopolized by the countries such as Japan, America and the like at present, and no mature technology exists in China.
In the currently adopted acetaldehyde condensation hydrogenation method, an intermediate 3-hydroxybutyraldehyde is generally generated, however, 3-hydroxybutyraldehyde has high viscosity and is not stable, and is decomposed when heated to about 85 ℃, toxic crotonaldehyde (crotonaldehyde) is easily generated by thermal dehydration in the production process, the crotonaldehyde simultaneously contains carbonyl and C ═ C double bonds, under the same condition of acetaldehyde condensation, the crotonaldehyde can be further condensed with other aldehydes to form a complex polymer, and the indexes of the product such as purity, smell, chromaticity and the like are greatly influenced while the product yield of 1, 3-butanediol is reduced. Due to the intense exothermic heat of condensation, the reactants yellow rapidly, resulting in product failure. Moreover, the existing process does not consider the influence of back mixing, and the crotonaldehyde generated in the reaction system can flow back to the reaction system again to be continuously condensed with other aldehydes, so that a plurality of byproducts are generated, and the color and taste indexes are not qualified. In addition, in the existing production process, due to the influence of complex factors such as improper raw material treatment, acetaldehyde escape, low acetaldehyde recovery rate, more byproducts, acetaldehyde hydrogenation in the subsequent process and the like, the final yield of the 1, 3-butanediol is low, the actual yield is usually below 75%, and the deodorization effect in the common process is not ideal enough.
Disclosure of Invention
The invention mainly aims to provide a method and a system for synthesizing 1, 3-butanediol, so as to overcome the defects of the prior art.
The embodiment of the invention provides a method for synthesizing 1, 3-butanediol (1,3-BDO), which comprises the following steps:
carrying out condensation reaction on a condensation reaction system containing uniformly mixed acetaldehyde and an alkali catalyst at the pH value of 9-12.8 at the temperature of 0-20 ℃ for 11 min-24 h to obtain a condensation product mainly containing 2,6-Dimethyl-1, 3-dioxane-4-ol (2,6-Dimethyl-1, 3-dioxane-4-ol, hereinafter abbreviated as DDO);
carrying out a cracking reaction on a cracking reaction system containing the 2,6-dimethyl-1, 3-dioxane-4-alcohol and a cracking catalyst at 50-110 ℃ for 1 min-5 h to obtain a cracking product mainly containing dimeric butyraldehyde (4-Hydroxy-alpha, 6-dimethyl-1,3-dioxane-2-ethanol, hereinafter abbreviated as HDDE);
and under the condition that the hydrogenation pressure is 1-15MPa, carrying out ring-opening hydrogenation reaction for 0.2-20 h at the temperature of 60-180 ℃ on a hydrogenation reaction system containing the dimeric butyraldehyde and a hydrogenation catalyst to prepare the 1, 3-butanediol.
Further, the condensation reaction is carried out in a protective atmosphere, particularly preferably a nitrogen atmosphere.
Further, the acetaldehyde comprises an acetaldehyde aqueous solution with the acetaldehyde content of 30-95 wt%.
Further, the content of acid in the acetaldehyde is below 0.05 wt%.
Further, the alkali catalyst comprises NaOH and Na2CO3、KOH、K2CO3、Na3PO4And sodium acetate, either alone or in combination.
Further, the DDO is a mixture of S and R enantiomers.
In some embodiments, the synthesis method further comprises: after the condensation reaction is finished, neutralizing the condensation reaction system with dilute acid, and then carrying out low-temperature flash evaporation treatment on the obtained reaction liquid.
Further, the pH value of the reaction liquid obtained after neutralization treatment is 6-8, and particularly preferably 6.2-7.5.
Further, the dilute acid comprises any one or a combination of more than two of acetic acid, phosphoric acid, dilute sulfuric acid and tartaric acid.
Further, the temperature of the low-temperature flash evaporation treatment is 20-78 ℃, particularly preferably 50-75 ℃, and the time is 1-60 min.
Further, the cracking catalyst comprises CeO2、TiO2、Al2O3MgO and SiO2Any one or a combination of two or more of them.
Further, the hydrogenation catalyst comprises a Ni-Pd/C catalyst containing trace precious metals.
Furthermore, the hydrogenation catalyst contains 1-30 wt% of Ni and 0.001-2 wt% of Pd.
In some embodiments, the synthesis method further comprises: and (3) carrying out separation treatment and refining treatment on the products of the ring-opening hydrogenation reaction.
The embodiment of the invention also provides a synthesis system of 1, 3-butanediol applied to the synthesis method, which comprises the following steps:
a condensation reaction unit capable of subjecting at least acetaldehyde and a base catalyst to a condensation reaction to produce a condensation product containing DDO;
a reactive distillation unit capable of at least subjecting the 2,6-dimethyl-1, 3-dioxane-4-ol and a cleavage catalyst to a cleavage reaction to produce a cleavage product comprising HDDE; and the number of the first and second groups,
and the ring-opening hydrogenation unit at least can carry out ring-opening hydrogenation reaction on the dimeric butyraldehyde and the hydrogenation catalyst to prepare the 1, 3-butanediol.
Further, the condensation reaction unit comprises a shell and tube reactor with built-in members, and the built-in members comprise spiral members.
In some embodiments, the synthesis system further comprises: a neutralization processing unit, a low-temperature flash evaporation processing unit, a separation processing unit and a refining processing unit.
Compared with the prior art, the invention has the advantages that:
1) the synthesis method of 1, 3-butanediol provided by the invention adopts a route of producing 1, 3-butanediol (1,3-BDO) from acetaldehyde through 2,6-dimethyl-1, 3-dioxane-4-alcohol, improves the stability of an intermediate product, improves the selectivity of 1, 3-butanediol, and reduces the generation of harmful crotonaldehyde and derivatives which are easy to develop color and smelly;
2) the synthesis system of 1, 3-butanediol provided by the invention adopts the tubular reactor with built-in components as the condensation reactor, so that the heat is effectively removed, the low-temperature cooling load is reduced, the reaction controllability is increased, unnecessary back mixing is reduced, and the generation of byproducts is reduced.
3) The invention adopts the mode of low-temperature flash evaporation and then catalytic reaction distillation to carry out 2,6-dimethyl-1, 3-dioxane-4-alcohol cracking and recover acetaldehyde, thereby effectively improving the utilization rate of raw materials and improving the yield of final products.
4) The invention adopts the ring-opening hydrogenation catalyst mainly comprising cheap metal, and has better economical efficiency.
5) The invention adopts the refining treatment of the adsorption tower to the final product, so that the chroma and the odor can meet the requirements of most high-end applications, and the application prospect is wide.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a process system for the synthesis of 1, 3-butanediol in an exemplary embodiment of the invention.
FIG. 2 is an infrared spectrum of the product obtained from the low temperature flash process in an exemplary embodiment of the invention.
FIG. 3 is a graph of an infrared spectrum of crotonaldehyde obtained with an exemplary embodiment of the present invention.
FIG. 4 shows a 400 MB NMR spectrum of a product obtained from a cryogenic flash process in an exemplary embodiment of the invention13C NMR chart.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have made extensive studies and extensive practices to propose a technical solution of the present invention. The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An aspect of an embodiment of the present invention provides a method for synthesizing 1, 3-butanediol (1,3-BDO), including:
carrying out condensation reaction on a condensation reaction system containing uniformly mixed acetaldehyde and an alkali catalyst at the pH value of 9-12.8 at the temperature of 0-20 ℃ for 11 min-24 h to prepare a condensation product mainly containing 2,6-dimethyl-1, 3-dioxane-4-alcohol;
carrying out a cracking reaction on a cracking reaction system containing the 2,6-dimethyl-1, 3-dioxane-4-alcohol and a cracking catalyst at the temperature of 50-110 ℃ for 1 min-5 h to prepare a cracking product mainly containing dimeric butyraldehyde;
and under the condition that the hydrogenation pressure is 1-15MPa, carrying out ring-opening hydrogenation reaction for 0.2-20 h at the temperature of 60-180 ℃ on a hydrogenation reaction system containing the dimeric butyraldehyde and a hydrogenation catalyst to prepare the 1, 3-butanediol.
Further, the condensation reaction is carried out in a protective atmosphere, particularly preferably a nitrogen atmosphere.
In some embodiments, the synthesis method may specifically comprise:
(1) mixing an aqueous solution containing 30-95% of acetaldehyde with an alkali catalyst solution, allowing the mixture to enter a condensation reactor for reaction, wherein the pH value of a reaction system is 9-12.8, a cooling bath is arranged outside a tubular reactor, the reaction time is 11 min-24 h, and a product mainly containing DDO is obtained after the reaction is finished. Wherein DDO is a mixture of S and R enantiomers, and the reaction is carried out under the protection of nitrogen in the whole reaction process.
Wherein the structural formula of the compound DDO is as follows:
Figure BDA0001611581430000051
further, the dosage of the alkali catalyst accounts for 0.05 wt% -1.50 wt% (mass fraction) of the total material.
In the step (1), further, the acid content in the acetaldehyde as the raw material is controlled to be below 0.05 wt%.
Further, the alkali catalyst is NaOH or Na2CO3、KOH、K2CO3、Na3PO4Sodium acetate or mixed solutions.
Further, in order to obtain more DDO and protect the hydroxyl in the 3-hydroxybutyraldehyde obtained by condensation in time by acetaldehyde, the reaction conditions should be comprehensively controlled, so that the condensation reaction rate should be as slow as possible, the pH value of the reaction environment should be optimized to 9.2-11.5, the temperature is controlled to 0-20 ℃, and the reaction time is prolonged to 1-20 hours.
In some embodiments, the synthesis method further comprises: and cooling the condensation reaction system by using a cooling medium while carrying out the condensation reaction.
Further, it is preferable that the condensation reactor is a shell and tube reactor having a mixing member built therein. Further, it is preferable that the built-in member is a spiral member, the cooling bath is provided outside the tubular reactor, the cooling bath medium is preferably water outside the tubular reactor, and the temperature range is 0 to 50 ℃, preferably 5 to 20 ℃.
In some embodiments, the synthesis method further comprises: after the condensation reaction is finished, neutralizing the condensation reaction system with dilute acid, and then carrying out low-temperature flash evaporation treatment on the obtained reaction liquid.
That is, the synthesis method further comprises: (2) and neutralizing the pH value of the reaction liquid to 6-8 by using dilute acid in a neutralization reaction tank.
In the step (2), the pH value is preferably 6.2-7.5, and the dilute acid is preferably acetic acid, phosphoric acid, dilute sulfuric acid, tartaric acid and the like. Preferably, a rapid stirring device is added during neutralization.
Further, the synthesis method comprises the following steps: (3) and (3) inputting the neutralized product into a low-temperature flash tank, wherein the temperature is 20-78 ℃, recovering unreacted acetaldehyde, and the residual liquid is crude DDO. The acetaldehyde at the top of the column is recovered and recycled to the reactor.
Further, different from other technologies, low-temperature flash evaporation is adopted in the step (3), preferably, the temperature is 50-75 ℃, and the time is 1-60 min, so that only free acetaldehyde is removed in the step, and the ring structure of DDO is not basically damaged.
Further, the synthesis method comprises the following steps: and (4) cracking the crude DDO at the bottom of the tower subjected to low-temperature flash evaporation in a reactive distillation device at the reaction temperature of 50-110 ℃ for 1 min-5 h. The reactive distillation device adopts a mode of coupling distillation and cracking reaction. The acetaldehyde obtained by cracking is recovered from the top of the column. The HDDE-based product is obtained after cracking.
Wherein the structural formula of HDDE is:
Figure BDA0001611581430000061
further, the mass of the cracking catalyst accounts for 1-15% of the total mass of the materials in the cracking reaction system.
Further, CeO is adopted in the cracking device2、TiO2、Al2O3MgO and SiO2As the cracking catalyst, water is used as a cracking promoter and a protective agent.
Further, the cracking degree is optimally controlled to be 50-95% due to the possibility of crotonaldehyde generation in the process of acetaldehyde removal protection.
Further preferably, the temperature of the cracking reaction is 60-80 ℃, and the cracking time is 5 min-2 h.
Preferably, the synthesis method further comprises: recovering acetaldehyde from the product of the cryogenic flash treatment or the product of the cracking reaction.
Further, the synthesis method further comprises: (5) in order to obtain a better hydrogenation raw material, the cracking product can be further separated, acetaldehyde is recovered, and crotonaldehyde and water are separated to obtain a purified hydrogenation raw material mainly containing HDDE.
Further, the synthesis method comprises the following steps: (6) and (3) feeding the product mainly containing HDDE in the step (5) into an open-loop hydrogenation reactor, and carrying out open-loop hydrogenation reaction on the product and hydrogen in the open-loop hydrogenation reactor, wherein the hydrogenation pressure is 1-15MPa, and the hydrogenation temperature is 60-180 ℃. Hydrogenation to obtain the crude alcohol product with 1, 3-butanediol as the main component.
Further, the mass of the hydrogenation catalyst accounts for 0.5-10% of the total mass of the materials in the hydrogenation reaction system.
Optimally, the hydrogenation catalyst is a Ni-Pd/C catalyst containing trace precious metals.
Further preferably, the hydrogenation pressure is 3-12 MPa, and the hydrogenation temperature is 60-180 ℃.
More preferably, the hydrogenation catalyst contains 1-30 wt% of Ni and 0.001-2 wt% of Pd.
Optimally, the Ni-Pd/C catalyst can be recovered from the product for recycling.
In some embodiments, the synthesis method further comprises: and (3) carrying out separation treatment and refining treatment on the products of the ring-opening hydrogenation reaction.
Further, the synthesis method further comprises: (7) and (3) feeding the hydrogenated product into a separation device, and removing light components, water, salt and heavy components to obtain a 1, 3-butanediol product.
Optimally, an atmospheric distillation tower is adopted for removing light components, the pressure is 0.1MPa, and a vacuum distillation tower is adopted for removing heavy components, the pressure is 0.0001MPa-0.1 MPa.
Still further, the synthesis method further comprises: (8) and (3) feeding the obtained 1, 3-butanediol product into an adsorption tower for refining treatment.
Optimally, 1, 3-butanediol product and a certain proportion of water are mixed and then enter an adsorption tower filled with active carbon for decolorization and deodorization treatment, and finally, rectification is carried out for removing water. Further optimally, the activated carbon meets the following criteria: the iodine adsorption value (mg/g) is 500-1000, the pH value is 6-8, the iron content is less than or equal to 0.010, and the chlorine content is less than or equal to 10 ppm.
Another aspect of embodiments of the present invention provides a system for synthesizing 1, 3-butanediol (1,3-BDO), comprising:
a condensation reaction unit capable of subjecting at least acetaldehyde and a base catalyst to a condensation reaction to produce a condensation product containing DDO;
a reactive distillation unit capable of at least subjecting the DDO and a cracking catalyst to a cracking reaction to produce a cracked product comprising HDDE; and the number of the first and second groups,
and the ring-opening hydrogenation unit at least can perform a ring-opening hydrogenation reaction on the HDDE and the hydrogenation catalyst to prepare the 1, 3-butanediol.
Further, the condensation reaction unit comprises a shell and tube reactor with built-in components.
Preferably, the internals member comprises a helical member.
Preferably, a cooling device for temperature reduction treatment is arranged outside the tubular reactor.
Further, the synthesis system further comprises: a neutralization processing unit, a low-temperature flash evaporation processing unit, a separation processing unit and a refining processing unit.
Further, the synthesis system comprises units such as premixing-condensation reaction-neutralization-flash evaporation-reactive distillation-separation-ring opening hydrogenation-separation-refining, unreacted acetaldehyde and acetaldehyde generated by cracking are recovered, and crotonaldehyde, ethanol, butanol and other products are by-produced in the system.
Referring to fig. 1, a process for synthesizing 1, 3-butanediol according to an exemplary embodiment of the present invention comprises:
mixing an aqueous solution containing acetaldehyde with an alkali catalyst, feeding the mixture into a premixing tank (A), uniformly mixing, and feeding the mixture into a condensation reactor (B) for reaction. The condensation reactor is a tubular reactor with a built-in spiral component, the pH value of a reaction system is 9-12.8, the reaction temperature is controlled at 0-20 ℃, and a product with 2,6-dimethyl-1, 3-dioxane-4-alcohol as a main component is obtained after the reaction is finished. The condensation product enters a neutralization reaction tank (C), and the pH value of the reaction solution is neutralized to 6-8 by dilute solution of acetic acid, phosphoric acid, sulfuric acid and tartaric acid. Feeding the neutralized product into a low-temperature flash tank (D) at 20-78 deg.C, recovering unreacted acetaldehyde, and feeding acetaldehyde to a separation unit (E) via a line (5). The infrared spectrum of the product (line 6) obtained by the cryogenic flash process is shown in FIG. 2, 400 Mm superconducting NMR13C NMR chart is shown in FIG. 4. The flash evaporation residual liquid is crude DDO, and enters a reaction distillation device (F) through a pipeline (6) for cracking, the reaction temperature is 50-110 ℃, and the reaction distillation device adopts a mode of coupling distillation and cracking reaction. The material containing acetaldehyde obtained by cracking is recovered from the top of the column through a line (14), crotonaldehyde and water are separated through a separation unit (E), and the acetaldehyde is circulated to the premixing tank through a line (13). The infrared spectrum of crotonaldehyde (line 16) obtained is shown in FIG. 3. The product mainly containing dimeric butyraldehyde obtained after cracking enters a separation unit (G) through a pipeline (7), the material after further separation enters an open-loop hydrogenation reactor (H) through a pipeline (8) and reacts with hydrogen under the action of a hydrogenation catalyst, the hydrogenation pressure is 1-15MPa, and the hydrogenation temperature is 60-180 ℃. And removing light components, water, salt and heavy components from the crude alcohol product obtained after hydrogenation by a separation unit (I) to obtain a 1, 3-butanediol product. In order to further improve the product quality and obtain a non-toxic, high-transparency and odorless product, the 1, 3-butanediol is subjected to a refining unit [ J ] to obtain the 1, 3-butanediol of the cosmetic grade.
The premixing tank is communicated with a condensation reactor, the condensation reactor is communicated with a neutralization reaction tank, the neutralization reaction tank is communicated with a low-temperature flash tank, the low-temperature flash tank is communicated with a reaction distillation device, the reaction distillation device is communicated with a separation unit, the separation unit is communicated with a ring-opening hydrogenation reactor, the ring-opening hydrogenation reactor is communicated with the separation unit, and the separation unit is communicated with a refining unit.
By the technical scheme, the synthesis method adopts a route of 2,6-dimethyl-1, 3-dioxane-4-alcohol to produce 1, 3-butanediol from acetaldehyde, improves the stability of an intermediate product, improves the selectivity of the 1, 3-butanediol, and reduces the generation of harmful crotonaldehyde and derivatives which are easy to develop color and smells.
The technical solution of the present invention will be described in further detail with reference to several preferred embodiments and the accompanying drawings, but the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were purchased from conventional biochemical reagent stores, unless otherwise specified.
Example 1 referring now to fig. 1, this example is an exemplary embodiment of a process flow system for producing 1, 3-butanediol from acetaldehyde.
Specifically, the process may include:
mixing an aqueous solution containing 85% of acetaldehyde with an alkali catalyst, and allowing the mixture to enter a tubular condensation reactor with a built-in spiral member for reaction. The acid content in acetaldehyde is controlled below 0.05 wt%, and the base catalyst is NaOH or Na2CO3、Na3PO4The pH value of the reaction system is 10.1, the reaction time is 10 hours, and the reaction temperature is controlled at 10 ℃. The outside of the tubular reactor is provided with a circulating water cooling bath, and the cooling is carried out in a counter-current manner, namely the flow direction of reactants at the inner side of the tubular reactor is opposite to the flow direction of cooling water, and a product with 2,6-dimethyl-1, 3-dioxane-4-alcohol as the main component is obtained after the reaction is finished. The condensation product was charged into a neutralization tank, and the reaction solution was neutralized to pH 6.8 with 5wt% phosphoric acid aqueous solution under rapid stirring. And (3) inputting the neutralized product into a low-temperature flash tank, wherein the temperature is 75 ℃, the time is 10min, and recovering unreacted acetaldehyde and recycling the unreacted acetaldehyde to the condensation reactor.
The residual liquid after flash evaporation is crude DDO, enters a reaction distillation device for cracking, and is arranged in the reaction distillation deviceIs pre-filled with TiO2The catalyst has the mass fraction of 1 percent, the reaction temperature of 80 ℃ and the reaction time of 1 h. The acetaldehyde produced by the cracking is recovered at the top of the apparatus and also recycled to the premix tank. Along with the reaction, because the device adopts the mode of distillation and cracking reaction coupling, remove the progression of pyrolysis reaction of cleavage product acetaldehyde, the bottom of the tower input water both as reaction medium and as entrainer simultaneously. Along with the reaction, the viscosity of the system is higher and higher, a product which is mainly dimeric butyraldehyde obtained after cracking enters a vacuum rectification tower, and the components (mass fraction) after vacuum rectification are 0.1% of acetaldehyde, 1.0% of crotonaldehyde, 20.9% of water, 6.0% of DDO, 71.1% of HDDE and 0.9% of other components.
The material after the vacuum distillation enters an open-loop hydrogenation reactor, and reacts with hydrogen under the action of a hydrogenation catalyst Ni-Pd/C, wherein the hydrogenation pressure is 5.5MPa, the hydrogenation temperature is 120 ℃, the mass fraction of the hydrogenation catalyst is 10%, and the reaction time is 1 h. The hydrogenation catalyst contains Ni 20 wt%, Pd 0.1 wt% and carbon carrier for the rest. The crude alcohol product obtained after hydrogenation contained 19.9% water, 2.1% ethanol, 1.0% butanol, 76.1% 1, 3-butanediol, and 0.9% other components. When water is not calculated, 1, 3-butanediol accounts for 95.0% of the total amount. And (3) separating relatively light components such as ethanol and butanol from the crude alcohol product through a series of separation devices, removing water, removing salt and heavy components to obtain the 1, 3-butanediol product. And a normal pressure rectifying tower is adopted for removing light components, and a reduced pressure rectifying tower is adopted for removing heavy components. The obtained 1, 3-butanediol product enters an adsorption tower filled with active carbon for refining and rectification again, and the active carbon meets the following standards: the iodine adsorption value is 500-1000mg/g, the pH value is 6-8, the iron content is less than or equal to 0.001, and the chlorine content is less than or equal to 10 ppm. Finally, by accounting, 0.92 ton of 1, 3-butanediol product can be produced and obtained from 1 ton of acetaldehyde raw material, meanwhile, chemical products such as crotonaldehyde, butanol and the like are by-produced, the purity of the refined 1, 3-butanediol can reach more than 99.5 wt% (water content is about 0.5 wt%), Sulfide (SO)4 2-Meter)<0.005 wt%, the chromaticity is detected by a Pt-Co method, the chromaticity of Pt-Co is less than or equal to 10APHA, and the odor is not generated.
Example 2
Will contain 8Mixing 3% acetaldehyde water solution and alkali catalyst, and reacting in tubular condensation reactor with built-in spiral member. The acid content in the acetaldehyde is controlled below 0.05 wt%, and the whole reaction process is carried out under the protection of nitrogen. The alkali catalyst is NaOH or Na3PO4The pH value of the reaction system is 10.0, the reaction time is 8h, and the reaction temperature is controlled at 0 ℃. Circulating water cooling bath is arranged outside the tubular reactor, and countercurrent cooling is carried out, namely the flow direction of reactants inside the tubular reactor is opposite to the flow direction of cooling water, and a product with 2,6-dimethyl-1, 3-dioxane-4-alcohol as the main component is obtained after the reaction is finished. The condensation product was charged into a neutralization tank, and the reaction solution was neutralized to pH 6.2 with 5wt% phosphoric acid aqueous solution under rapid stirring. Feeding the neutralized product into a low-temperature flash tank at 68 deg.C for 15min, recovering unreacted acetaldehyde, and recycling to the condensation reactor.
The residual liquid after flash evaporation is crude DDO, and enters a reaction distillation device for cracking, wherein TiO is pre-filled in the reaction distillation device2The catalyst has the mass fraction of 5 percent, the reaction temperature of 65 ℃ and the reaction time of 1.5 h. The acetaldehyde produced by the cracking is recovered at the top of the apparatus and also recycled to the premix tank. Along with the reaction, because the device adopts the mode of distillation and cracking reaction coupling, remove the progression of pyrolysis reaction of cleavage product acetaldehyde, the bottom of the tower input water both as reaction medium and as entrainer simultaneously. Along with the reaction, the viscosity of the system is higher and higher, a product which is mainly dimeric butyraldehyde obtained after cracking enters a vacuum rectification tower, and the components (mass fraction) after vacuum rectification are 0.1% of acetaldehyde, 1.2% of crotonaldehyde, 21.1% of water, 19.0% of DDO, 57.6% of HDDE and 1.0% of other components.
The material after the vacuum distillation enters an open-loop hydrogenation reactor, and reacts with hydrogen under the action of a hydrogenation catalyst Ni-Pd/C, wherein the hydrogenation pressure is 3.9MPa, the hydrogenation temperature is 100 ℃, the mass fraction of the hydrogenation catalyst is 1%, and the reaction time is 7 h. The hydrogenation catalyst contains Ni 15 wt%, Pd 0.1 wt% and carbon carrier for the rest. The crude alcohol product obtained after hydrogenation contains 20.5% water, 6.5% ethanol, 1.3% butanol, 70.6% 1, 3-butanediol, and 11% of other components. When water is not calculated, 1, 3-butanediol accounts for 88.8% of the total. And (3) separating relatively light components such as ethanol and butanol from the crude alcohol product through a series of separation devices, removing water, removing salt and heavy components to obtain the 1, 3-butanediol product. And a normal pressure rectifying tower is adopted for removing light components, and a reduced pressure rectifying tower is adopted for removing heavy components. The obtained 1, 3-butanediol product enters an adsorption tower filled with active carbon for refining and rectification again, and the active carbon meets the following standards: the iodine adsorption value is 500-1000mg/g, the pH value is 6-8, the iron content is less than or equal to 0.001, and the chlorine content is less than or equal to 10 ppm. Finally, by accounting, 0.85 ton of 1, 3-butanediol product can be produced and obtained from 1 ton of acetaldehyde raw material, meanwhile, chemical products such as crotonaldehyde, butanol and the like are by-produced, the purity of the refined 1, 3-butanediol can reach more than 99.5 wt% (water content is about 0.5 wt%), Sulfide (SO)4 2-Meter)<0.005 wt%, Pt-Co chroma less than or equal to 8APHA, and no odor.
Example 3
Mixing an aqueous solution containing 50% of acetaldehyde with an alkali catalyst, and allowing the mixture to enter a tubular condensation reactor for reaction. Controlling the acid content in acetaldehyde below 0.05 wt%, and using KOH and Na as base catalyst3PO4With Na2CO3The pH value of the solution and the reaction system is 10.8, and the reaction time is 5 h. Circulating water cooling bath is arranged outside the tubular reactor, countercurrent cooling is carried out, the temperature is controlled at 20 ℃, after the reaction is finished, condensation products enter a neutralization tank, and the pH value of a reaction solution is neutralized to 6.0 by using 5wt% dilute acetic acid aqueous solution under the condition of rapid stirring. Feeding the neutralized product into a low-temperature flash tank at 70 deg.C for 15min, recovering unreacted acetaldehyde, and recycling to the condensation reactor. The residual liquid after flash evaporation is crude DDO, and enters a reaction distillation device for cracking, and neutral mesoporous TiO is pre-filled in the reaction distillation device2-SiO2The catalyst has the mass fraction of 15 percent, the reaction temperature of 70 ℃ and the reaction time of 0.5 h. The acetaldehyde produced by the cracking is recovered at the top of the apparatus and also recycled to the premix tank. And (3) treating the cracked product in a reduced pressure rectifying tower, feeding the treated product into an open-loop hydrogenation reactor, and hydrogenating the product at the pressure of 10MPa and the temperature of 80 ℃ by using 30wt% of Ni-0.02 wt% of Pd/C as a catalyst, wherein the mass fraction of the hydrogenation catalyst is 0.5%, and the reaction time is 20 hours. Through separation and refiningThe prepared product can produce 0.82 ton of 1, 3-butanediol product per 1 ton of acetaldehyde raw material, the purity of the refined 1, 3-butanediol can reach more than 99.5 wt% (water content is about 0.5 wt%), the chromaticity of Pt-Co is less than or equal to 10APHA, and the product has no odor.
Example 4
Mixing an aqueous solution containing 30% of acetaldehyde with an alkali catalyst, and allowing the mixture to enter a tubular condensation reactor for reaction. Controlling the acid content in acetaldehyde below 0.05 wt%, and using KOH and Na as base catalyst3PO4And K2CO3The pH value of the solution and the reaction system is 9.0, the pressure is 0.3MP, and the reaction time is 24 h. The outside of the tubular reactor is provided with a circulating water cooling bath, the cooling is carried out in a countercurrent way, the temperature is controlled at 50 ℃, after the reaction is finished, the condensation product enters a neutralization tank, and the pH value of the reaction solution is neutralized to 7.5 by using a 5 percent dilute sulfuric acid aqueous solution under the condition of rapid stirring. Feeding the neutralized product into a low-temperature flash tank at 78 deg.C for 1min, recovering unreacted acetaldehyde, and recycling to the condensation reactor. The residual liquid after flash evaporation is crude DDO, and enters a reaction distillation device for cracking, and neutral mesoporous TiO is pre-filled in the reaction distillation device2-Al2O3The catalyst has the mass fraction of 1 percent, the reaction temperature of 50 ℃ and the reaction time of 2 hours. The acetaldehyde produced by the cracking is recovered at the top of the apparatus and also recycled to the premix tank. And (3) treating the cracked product in a reduced pressure rectifying tower, feeding the treated product into an open-loop hydrogenation reactor, and hydrogenating by using 1 wt% of Ni-2 wt% of Pd/C catalyst under the pressure of 1MPa and the temperature of 180 ℃, wherein the mass fraction of the hydrogenation catalyst is 10%, and the reaction time is 10 h. The product is obtained after separation and refining, 0.72 ton of 1, 3-butanediol product can be produced and obtained from 1 ton of acetaldehyde raw material, the purity of the refined 1, 3-butanediol can reach more than 99.5 wt% (water content is about 0.5 wt%), the chromaticity of Pt-Co is 30APHA, and the product has slight odor.
Example 5
Mixing an aqueous solution containing 95% of acetaldehyde with an alkali catalyst, and allowing the mixture to enter a tubular condensation reactor for reaction. Controlling the acid content in acetaldehyde below 0.05 wt%, and using KOH and Na as base catalyst3PO4The pH value of the solution and the reaction system is 12.8, and the reaction time is 11 min. The outside of the tubular reactor is provided with a circulating water cooling bath for countercurrent coolingThe temperature is controlled at 5 ℃, after the reaction is finished, the condensation product enters a neutralization tank, and the pH value of the reaction solution is neutralized to 8 by 5 percent acetic acid aqueous solution under the condition of rapid stirring. Feeding the neutralized product into a low-temperature flash tank at 20 deg.C for 60min, recovering unreacted acetaldehyde, and recycling to the condensation reactor. The residual liquid after flash evaporation is crude DDO, and enters a reaction distillation device for cracking, and modified mesoporous SiO is pre-installed in the reaction distillation device2-CeO2The catalyst has a mass fraction of 10%, a reaction temperature of 110 ℃ and a reaction time of 1 min. The acetaldehyde produced by the cracking is recovered at the top of the apparatus and also recycled to the premix tank. After cracking, decompression and rectification tower and hydrogenation at the pressure of 15MPa and the temperature of 60 ℃, the mass fraction of 1 wt% Ni-2 wt% Pd/C catalyst of the hydrogenation catalyst is 10%, and the reaction time is 0.2 h. After separation and refining, 0.51 ton of 1, 3-butanediol product and 50APHA of Pt-Co chroma can be produced and obtained from 1 ton of acetaldehyde raw material.
Example 6
The other conditions were the same as in example 3, the pH in the condensation reactor was changed to 10.2, the reaction time was 3 hours, and the reaction temperature was controlled at 15 ℃. The neutralization tank neutralized the reaction solution to pH 8.0 with a 5wt% aqueous solution of tartaric acid. The catalyst in the reactive distillation device is Al2O3MgO, the mass fraction of which is 5 percent, the temperature is 70 ℃, and the time is 0.3 h. In the hydrogenation step, the catalyst is 30wt% Ni-0.001 wt% Pd/C, the mass fraction of the catalyst is 10%, after separation and refining after hydrogenation, 0.80 ton of 1, 3-butanediol product can be produced per 1 ton of acetaldehyde raw material, the purity of the refined 1, 3-butanediol can reach more than 99.5 wt% (water content is about 0.5 wt%), the chromaticity of Pt-Co is less than or equal to 10APHA, and the catalyst has no odor.
Example 7
Other conditions were the same as in example 3, NaOH and Na were used in the condensation reactor3PO4And the mixed solution of the sodium acetate is used as a catalyst, the pH value is 10.8, the reaction time is 2 hours, and the reaction temperature is controlled at 10 ℃. The neutralization tank neutralizes the reaction solution to 7.8 by using 5wt% dilute acetic acid aqueous solution. The mass fraction of the catalyst in the reactive distillation device is 1 percent, the temperature is 60 ℃, and the time is 1 h. Hydrogenation, separation and refining are carried out to obtain the product, 0.81 ton of 1, 3-butanediol product and 1 after refining can be obtained from 1 ton of acetaldehyde raw material,the purity of 3-butanediol can reach more than 99.5 wt% (water content is about 0.5 wt%), the chromaticity of Pt-Co is less than or equal to 10APHA, and no odor is generated.
Example 8
The other conditions were the same as in example 3, the pH in the condensation reactor was changed to 11.0, the reaction time was 1 hour, and the reaction temperature was controlled at 18 ℃. The neutralization tank neutralized the reaction solution to pH 7.0 with a 5wt% dilute aqueous sulfuric acid solution. The mass fraction of the catalyst in the reactive distillation device is 8 percent, the temperature is 50 ℃, and the time is 5 hours. The product is obtained after hydrogenation, separation and refining, 0.82 ton of 1, 3-butanediol product can be obtained from 1 ton of acetaldehyde raw material, the purity of the refined 1, 3-butanediol can reach more than 99.5 wt% (water content is about 0.5 wt%), the chromaticity of Pt-Co is less than or equal to 20APHA, and the product has no odor.
Comparative example 1
The method comprises the steps of enabling an aqueous solution containing 88% of acetaldehyde and a NaOH catalyst to enter a continuous stirred tank reactor to be uniformly mixed for reaction, keeping the pH value at 12.8, enabling a freezing solution at the temperature of-10 ℃ to pass through a reactor jacket to keep the reaction temperature at 10 ℃ due to violent reaction, dropwise adding 5wt% of dilute acetic acid after reaction for 10min till the pH value is neutral, then performing flash evaporation at the temperature of 80 ℃, adding a residual liquid into a high-pressure kettle, performing hydrogenation for 1h under the hydrogen pressure of 6MPa by using Raney nickel as a catalyst, separating water, ethanol and butanol from the reaction liquid through a series of flash evaporation and the like to obtain a viscous liquid product, wherein the yield is 0.58 ton/ton of acetaldehyde. The Pt-Co color of the final product is about 100APHA, and the final product has slight smell.
Comparative example 2
An aqueous solution containing 85% acetaldehyde and an alkali catalyst were mixed and fed into a continuous stirred tank reactor to carry out a reaction under the same conditions as in example 1. In the reaction process, obvious heat release and difficult heat transfer in the reaction kettle are found, the reaction temperature continuously rises, bubbles can be observed in the kettle, the reaction kettle can be suspended only when the alkali catalyst is added, and the reaction kettle can be continued after cooling.
The yield of the 1, 3-butanediol product is reduced from 0.92 ton/ton to 0.68 ton/ton, the content of crotonaldehyde and butanol serving as byproducts is increased, and the chromaticity of the Pt-Co final product is increased from less than or equal to 10APHA to about 30APHA, so the product has slight odor.
Comparative example 3
The other conditions are the same as the example 1, but the materials after the flash evaporation at the temperature of 75 ℃ directly enter a ring-opening hydrogenation reactor for hydrogenation (the materials after the flash evaporation do not enter a reactive distillation device for cracking). The yield of the 1, 3-butanediol product is reduced from 0.92 ton/ton to 0.6 ton/ton, and the by-product contains a large amount of ethanol, so that the economic efficiency is poor.
Comparative example 4
The other conditions are the same as the example 1, but the materials after the flash evaporation at the temperature of 100 ℃ directly enter a ring-opening hydrogenation reactor for hydrogenation (the materials after the flash evaporation do not enter a reactive distillation device for cracking). The yield of the 1, 3-butanediol product is reduced from 0.92 ton/ton to 0.62 ton/ton, and the by-products contain a large amount of ethanol and butanol, so that the economic efficiency is poor.
Comparative example 5
The other conditions were the same as in example 1, but the acid content in the acetaldehyde as the starting material was not controlled (the acid content in the acetaldehyde as the starting material was 0.9 wt% by titrimetric analysis). The yield of the 1, 3-butanediol product is reduced from 0.92 ton/ton to 0.69 ton/ton, and the economical efficiency is poor.
Comparative example 6
The other conditions were the same as in example 1, but with pure acetaldehyde as starting material, no reaction was found at the lower pH (10.1). After raising the reaction pH to 12.5 and reacting for 15min (other conditions are the same as in example 1), the catalyst is found to be solidified at the bottom in the reaction process, the yield of the 1, 3-butanediol serving as a final product is reduced from 0.92 ton/ton to 0.67 ton/ton, the product is yellow, and the maximum Pt-Co color number is 100 APHA.
In addition, the inventor also refers to the mode of examples 1-8, tests are carried out by using other raw materials and conditions listed in the specification, the corresponding effect can be achieved, the yield of the synthesis method is high, the 1, 3-butanediol with high product quality is obtained, and the method is suitable for industrial production and has wide application prospect.
In conclusion, the synthesis method of the invention adopts a route of producing 1, 3-butanediol from acetaldehyde via 2,6-dimethyl-1, 3-dioxane-4-ol, improves the stability of an intermediate product, improves the selectivity of the 1, 3-butanediol and reduces the generation of harmful, chromophoric and smelly crotonaldehyde and derivatives. The invention adopts the refining treatment of the adsorption tower to the final product, so that the chroma and the odor can meet the requirements of most high-end applications, and the application prospect is wide.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that the above-mentioned embodiments are only illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (22)

1. A method for synthesizing 1, 3-butanediol is characterized by comprising the following steps:
carrying out condensation reaction on a condensation reaction system containing uniformly mixed acetaldehyde and an alkali catalyst at the pH value of 9-12.8 at the temperature of 0-20 ℃ in a protective atmosphere for 11 min-24 h to prepare a condensation product mainly containing 2,6-dimethyl-1, 3-dioxane-4-alcohol, wherein the content of acid in the acetaldehyde is below 0.05 wt%;
after the condensation reaction is finished, neutralizing the condensation reaction system with dilute acid, and then carrying out low-temperature flash evaporation treatment on the obtained reaction liquid, wherein the temperature of the low-temperature flash evaporation treatment is 20-78 ℃ and the time is 1-60 min;
cracking reaction is carried out on a cracking reaction system containing the 2,6-dimethyl-1, 3-dioxane-4-alcohol and a cracking catalyst for 1 min-5 h at 50-110 ℃, so as to obtain a cracking product mainly containing dimeric butyraldehyde, wherein the mass of the cracking catalyst accounts for 1-15% of the total mass of the cracking reaction system, and the cracking catalyst is selected from CeO2、TiO2、Al2O3MgO and SiO2The cracking reaction system also comprises a cracking promoter and a protective agent, wherein the cracking promoter and the protective agent are water;
and under the condition that the hydrogenation pressure is 1-10 MPa, carrying out ring-opening hydrogenation reaction for 0.2-20 h at 60-180 ℃ on a hydrogenation reaction system containing the dimeric butyraldehyde and a hydrogenation catalyst to obtain the 1, 3-butanediol, wherein the mass of the hydrogenation catalyst accounts for 0.5-10% of the total mass of the hydrogenation reaction system, the hydrogenation catalyst is a Ni-Pd/C catalyst containing trace precious metals, and the content of Ni and Pd in the hydrogenation catalyst are respectively 1-30 wt% and 0.001-2 wt%.
2. The method of synthesis according to claim 1, characterized in that: the protective atmosphere is a nitrogen atmosphere.
3. The method of synthesis according to claim 1, characterized in that: the acetaldehyde is derived from an acetaldehyde aqueous solution with an acetaldehyde content of 30-95 wt%.
4. The method of synthesis according to claim 1, characterized in that: the alkali catalyst is selected from NaOH and Na2CO3、KOH、K2CO3、Na3PO4And sodium acetate, either alone or in combination.
5. The method of synthesis according to claim 1, characterized in that: the pH value of the condensation reaction system is 9.2-11.5.
6. The method of synthesis according to claim 1, characterized in that: the time of the condensation reaction is 1-20 h.
7. The method of synthesis according to claim 1, characterized in that: the 2,6-dimethyl-1,3-dioxan-4-ol is a mixture of the S and R enantiomers.
8. The method of synthesis of claim 1, further comprising: and cooling the condensation reaction system by using a cooling medium while carrying out the condensation reaction.
9. The method of synthesis according to claim 8, characterized in that: the cooling medium is water.
10. The method of synthesis according to claim 8, characterized in that: the temperature of the cooling medium is 0-50 ℃.
11. The method of synthesis according to claim 10, characterized in that: the temperature of the cooling medium is 5-20 ℃.
12. The method of synthesis according to claim 1, characterized in that: and the pH value of the reaction liquid obtained after neutralization treatment is 6-8.
13. The method of synthesis according to claim 12, characterized in that: the pH value of the reaction liquid obtained after neutralization treatment is 6.2-7.5.
14. The method of synthesis according to claim 1, characterized in that: the dilute acid is selected from any one or combination of more than two of acetic acid, phosphoric acid, dilute sulfuric acid and tartaric acid.
15. The method of synthesis according to claim 1, characterized in that: the temperature of the low-temperature flash evaporation treatment is 50-75 ℃.
16. The method of synthesis according to claim 1, characterized in that: the temperature of the cracking reaction is 60-80 ℃, and the time is 5 min-2 h.
17. The method of synthesis of claim 1, further comprising: recovering acetaldehyde from the product of the cryogenic flash treatment or the product of the cracking reaction.
18. The method of synthesis according to claim 1, characterized in that: the hydrogenation pressure in the ring-opening hydrogenation reaction is 3-12 MPa.
19. The method of synthesis of claim 1, further comprising: and (3) carrying out separation treatment and refining treatment on the products of the ring-opening hydrogenation reaction.
20. The method of synthesis of claim 19, wherein: the separation treatment comprises normal pressure rectification treatment and vacuum rectification treatment.
21. The method of synthesis of claim 20, wherein: the pressure of the atmospheric distillation treatment is 0.1MPa, and the pressure of the vacuum distillation treatment is 0.0001-0.1 MPa.
22. The synthesis method according to claim 19, wherein the refining treatment comprises: and (3) carrying out decoloration and deodorization treatment on the 1, 3-butanediol, and then carrying out rectification for removing water.
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